Arylazo-iminoisoindolinone dyestuffs

ABSTRACT

Iminoisoindolinone dyestuffs of the formula   WHEREIN R denotes an aromatic radical, R1 denotes a H or chlorine atom, an alkyl, alkoxy, hydroxyalkoxy or alkoxyalkoxy group containing 1 to 4 carbon atoms, or a phenoxy, phenalkoxy, phenalkoxyalkoxy or phenoxyalkoxy group and the X denote halogen atoms, are provided. The dyestuffs are valuable pigments which may be used for pigmenting high molecular organic materials such as cellulose, ethers, polyamides or polyesters. The pigments possess high fastness properties, especially excellent fastness to light, migration and weathering.

United States Patent Model et 211.

Oct. 14, 1975 ARYLAZO-IMINOISOINDOLINONE DYESTUFFS Inventors: Ernst Model, Basel; Jost von der Crone; Andre Pugin, both of Riehen, all of Switzerland Assignee: Ciba-Geigy Corporation, Ardsley,

Filed: Sept. 13, 1972 Appl. No.: 288,620

Foreign Application Priority Data Sept. 27, 1971 Switzerland 14053/71 US. Cl. 260/165; 106/288 Q; 260/152; 260/205; 260/206; 260/207; 260/207. 1; 260/326 HL Int. Cl. C09B 43/00 Field of Search 260/ 165, 152

References Cited UNITED STATES PATENTS 2/1961 Pugin 260/165 X 3/1965 Sureau et a1 12/1967 Sureau et a1 8/1972 Padmanathan 260/ 165 X Primary ExaminerFloyd D. Higel Attorney, Agent, or FirmVincent .l. Cavalieri [5 7 ABSTRACT lminoisoindolinone dyestuffs of the formula X ll 11 X wherein R denotes an aromatic radical, R denotes a H or chlorine atom, an alkyl, alkoxy, hydroxyalkoxy or alkoxyalkoxy group containing 1 to 4 carbon atoms, or a phenoxy, phenalkoxy, phenalkoxyalkoxy or phenoxyalkoxy group and the X denote halogen atoms, are provided. The dyestuffs are valuable pigments which may be used for pigmenting high molecular organic materials such as cellulose, ethers, polyamides or polyesters. The pigments possess high fastness properties, especially excellent fastness to light, migration and weathering.

9 Claims, No Drawings ARYLAZO-IMINOISOINDOLINONE DYESTUFFS It has been found that new valuable iminoisoindolinone dyestuffs of the formula wherein R denotes an aromatic radical, R, denotes H or a chlorine atom, an alkyl, alkoxy, hydroxyalkoxy or alkoxyalkoxy group containing 1-4 carbon atoms or a phenoxy, phenalkoxy, phenalkoxyalkoxy or phenoxyalkoxy group and the X denote halogen atoms, are obtained if an azo compound of the formula wherein R and R, have the indicated meaning is condensed in the molar ratio of 1:2 with a 4,5,6.7-tetrahalogenoisoindolinone-l which in the 3-position contains easily replaceable substituents which, depending on their nature or number, require two bonds and are more mobile than the oxygen present in the l-position.

In the dyestuffs according to the invention, R preferably corresponds to a benzene radical. Particular interest attaches to dyestuffs of the formula (III) wherein R denotes a H atom or a methoxy group, X denotes a hydrogen or halogen atom or an alkyl, alkoxy, trifluoromethyl, acylamino, carboxylic acid ester or carboxylic' acid amide group, and Y and Z denote hydrogen or halogen atoms or alkyl or alkoxy groups 2 containing lto 4 carbon atoms, and especially those of the formula wherein R denotes a H atom or a methoxy group and Y, and Z, denote hydrogen or halogen atoms or alkyl or alkoxy groups containing l to 4 carbon atoms, or those of the formula wherein R Y, and Z, have the indicated meanings and R denotes an alkyl group, containing 1 to 3 carbon atoms, or a phenyl radical optionally substituted by halogen atoms or alkyl or alkoxy groups containing 1 to 4 carbon atoms, or those of the formula wherein R;,, Y, and Z, have the indicated meaming, X

and Y denote hydrogen or halogen atoms or alkyl or 3 alkoxy groups containing 1 to 4 carbon atoms, or triflu oromethyl groups, and 2;, denotes a hydrogen or halogen atom or an alkyl or alkoxy group containing 1 to 4 carbon atoms.

The starting substances used are, for example,

4,5,6,7-tetrabromo-isoindolines but preferably 4,5,6, 7- i tetrachloro-isoindolines. As easily replaceable substituents in the 3-position they contain, for example, two halogen atoms, especially chlorine atoms, two secondary amino groups, for example those containing l to 4 carbon atoms, for example piperidino or morpholino groups, an imino or a thio group or especially 2 alkoxy groups, for example those containing 1 to 4 carbon atoms, especially methoxy groups. These starting substances are known.

The azo compounds used are preferably those of the formula wherein R X, Y and Z have the indicated meaning and especially those of the formula wherein R Y and Z, have the indicated meanings,

wherein R R Y, and Z have the indicated meaning, or those of the formula 1 R 5 -N=N- 4W -HN-CO I. Z NR2 dibromoaniline,

line, 2,5-dimethylaniline, v2-methyl-5-chloroaniline, 2- tmethyl-4-chloroaniline, 2-methyl-3-chloroaniline, 2-

chloro-5-trifluoromethylaniline, 3-trifluoromethylaniline, 3,5 bis-trifluoromethylaniline, 2-chloro-5-trifluoromethylaniline, 2- and 4-methoxyaniline, 3- chloro-4-methoxyaniline, '2-methoxy-5-chloroaniline, 2,5-dimethoxy-4-chloroaniline, 2-methoxy-5-trifluoromethylaniline, 2-amino-4-trifluoromethyl-4'- chlorodiphenyl-ether, 2-amino-4-trifluoromethyldiphenyl-ether, 2-amino-4-chl0ro-diphenyl-ether, 2-amino- 2,4-dichloro-diphenyl-ether, 2-amino-4,4-dichlorodiphenyl-ether, l-aminobenzene-2-carboxylic acid methyl ester, l-aminobenzene-2-carboxylic acid ethyl ester, l-aminobenzene-2-chloro-5-carboxylic acid methyl ester, 1-amino-2-methylbenzene-5-carboxylic acid methyl ester, l-amino-2-chlorobenzene-5-carboxylic acid methylamide, 4-methyl-3-aminobenzoic acid amide, 4-chloro-3-aminobenzoic acid amide, 2,4- dichloro-S-aminobenzoic acid amide, 4-methoxy-3- aminobenzoic acid amide, 4-methyl-3-aminobenzoic acid 2'-chloro-5-trifluoromethylaniline, 4-chloro-3- aminobenzoic acid 2,5-dichloroanilide, 4-chloro-3- aminobenzoic acid 2-chloro-5 '-carbomethoxyanilinde, 4-chloro-3-aminobenzoic acid 3-chloroanilide, 2,4-dichloro-5-aminobenzoic acid 2,5- dichloroanilide, 2,4-dichloro-S-aminobenzoic acid 3- trifluoromethylanilide, 2,4-dichloro-5-aminobenzoic acid 3-chloroanilide, 5-amino-4-methoxy-2- chlorobenzoic acid 3-trifluoromethylanilide, 4- methoxy-3-aminobenzoic acid 3'-chloroanilide, 4-

methoxy-3-aminobenzoic acid 2,5-dichloroanilide, 4-carbomethoxy-3-aminobenzoic acid anilide, 4- methoxy-3-aminobenzoic acid 3-trifluoromethylanilide, 4-carboethoxy-3-aminobenzoic acid 2,5- dichloroanilide, 4-aminobenzoic acid 2,4- dichloroanilide, 4-aminobenzoic acid 2'-chloro-'5-trifluoromethylanilide, 4-amino-3-methylbenzoic acid 3'- trifluoromethylanilide, 4-amino-3-methylbenzoic acid 4'-chloroanilide, 4-benzoylamino-aniline, 2,5-dichloro- 4-ben zoylaminoa niline, 2,5-dichloro-4-(4'-chlorobenzoylamino)-aniline, 2,5-dichloro-4-(2,4-dichlorobenzoylamino )-aniline, 2,5-dichloro-4-( 2,5 -dichlorobenzoylamino)-aniline, 2,5-dichloro-4-(4-methylbenzoylamino)-ani line, 2,5-dichloro-4-(4-phenylbenzoylamino)-aniline, 2,5-dimethyl-4-benzoylamino-aniline, 2,5-dimethyl-4-(4'-chlorobenzoylamino)-aniline, 2,5-dimethyl-4-( 2',4 -dichlorobenzoylamino )-aniline,

2,5-dimethyl-4-( 2,5 -dichlorobenzoylamino )-aniline,

2,5-dimethyl-4-(4-methylbenzoylamino)-aniline, 2,5- dimethyl-4-(4'-methoxybenzoylbenzoyl-amino)-aniline, 2-chloro-5-methyl-4-benzoylamino-aniline,

chloro-5-methyl-4-(4'-chlorobenzoylamino)-aniline, 2-chloro-5-methyl-4-( 2 ,5 -dichlorobenzoylamino aniline, 2-chloro-5-methyl-4-(4'-methylbenzoylamino)-aniline, 2-chl0ro-5-methyl-4-(4-phenylbenzoylamino )-aniline, 2-methoxy-5-chloro-4-( benzoylamino)-aniline, 2-methoxy-5-chloro-4-(4'- chlorobenzoylamino)-aniline, 2-methoxy-5-chloro-4- (2,5-dichlorobenzoylamino)-aniline, 2-methoxy-5- chloro-4-(4-methoxylbenzoylamino)-aniline, 2- methoxy-5-chloro-4-(4-phenylbenzoylamino)-aniline, 4-(4-carbomethoxy)-benzoylamino-aniline, 3,5- dimethyl-4-acetylaminoaniline, 3,5-dimethyl-4-(4'- chlorobenzoylamino)-aniline, 3,5-dichloro-4- 'acetylaminoanilineand .3,5-dichloro-4-(4-chlorobenzoylamino)-aniline. l

and if necessary with 'warming the' 'intim'ately mixed components, particularly advantageously in the presence of organic solvents which are inert, that is to say which do not participate in the reaction.

1f starting from 3-imino-, 3-thioor 3,3-bis-tert.- amino-4,5,6,7-tetrachloroisoindolin-l-ones or from alkali salts of 3,3-dialkoxy-4,5,6,7-tetrachloroisoindolinl-ones, organic solvents which are miscible with water are advantageously used, for example lower aliphatic alcohols, such as lower alkanols, for example methanol, isopropanol or butanol, lower cyclic ethers, such dioxane or ethylene glycol monomethyl ether and lower aliphatic ketones, such acetone. Condensation here already takes place at relatively low temperatures. Avantageously, the reaction is carried out in the presence of agents which bind bases; as examples of such, there may be mentioned lower fatty acids which then simultaneously act as solvents, especially acetic acid.

If using 3,3-dihalogeno-4,5,6,7-tetrachloro-isoindolin-l-ones, organic solvents which are free of hydroxyl groups, such as hydrocarbons, for example aromatic hydrocarbons, such as benzene, toluene, xylene, tetrahydronaphthalene or diphenyl or cycloaliphatic hydrocarbons, for example cyclohexane, and also halogenated hydrocarbons, such as aliphatic hydrocarbons, for example carbon tetrachloride or tetrachloroethylene, or aromatic hydrocarbons, such as chlorobenzene or dichlorobenzenes and trichlorobenzenes, and also aromatic nitrohydrocarbons, such nitrobenzene, ethers, namely aliphatic ethers, such as dibutyl ether, aromatic ethers, such as diphenyl ether, or cyclic ethers, such as dioxane, and also ketones, such as acetone, or esters, especially esters of lower fatty acids with lower alkanols, such as ethyl acetate, in the presence of acid-binding agents, are preferred.

The new pigment precipitates from the reaction medium' directly after it is formed. For certain purposes this can be used directly as the crude pigment; it can however also be improved yet further in its properties,

especially as regards purity, form and covering power,

according to methods which are in themselves known, for example by extraction with organic solvents or by grinding with grinding auxiliaries which can subsequently be removed again, for example salts.

The new dyestuffs are valuable pigments which in a finely divided form can be used for pigmenting high molecular organic material, for example cellulose ethers and cellulose esters, such as ethylcellulose, acetylcellulose or nitrocellulose, polyamides or polyurethanes or polyesters, natural resins or synthetic resins, for example aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, thermoplastic or thermosetting acrylic'resins, rubber, casein, silicone and silicone resins, individually or as mixtures. 1t is im- -material whether the high molecular compounds mentioned are in the form of plastic masses or melts or in the foml of spinning solutions, lacquers, paints or printing inks. Depending on the end use, it proves advantageous to employ the new pigments as toners or in the form of preparations. The new pigments are distinguished by high fastness properties, especially by excellent fastness to light, migration and weathering.

r 6] 7 EXAMPLE 1 A hot solution of 5.3 g bf 2,4-diaminobenzene in 200 ml of o-dichlorobenzene is added, with good stirring, to a solution of 17 g of 3,3,4,5,6,7-hexachloroisoindolinl-one in ml of o-dichlorobenzene. A yellow precipitate immediately forms. The suspension is heated to 150 T 160C and is kept at this temperature for 2 hours, whilst stirring. The insoluble dyestuff is filtered off at C and washed with alcohol, acetone and water. After drying, 13 g of a yellow pigment having excellentfastness properties are obtained, which can be used without further after-treatment and in lacquers gives yellow colourations of excellent fastness to light and to weathering.

EXAMPLE 2 20 g of 3,4,5,6-tetrachloro-2-cyanobenzoic acid methyl ester are stirred with 68.5 ml of a 1 N sodium methylate solution in methanol to give a clear solution. The] sodium salt of 3,3-dimethoxy-4,5,6,7-tetrachloroisoindolinl-one is thereby produced. 7 g of 2,4- diamino-3,4-dichloroazobenzene and 100 ml of odichlorobenzene are now stirred in. The reaction mixture is heated to 100C whilst distilling off methanol and stirring well. After adding a further 100 ml of odichlorobenzene and 24 ml of glacial acetic acid, the temperature is raised to C and maintained for 2 hours. The insoluble dyestuff is filtered off at 120C and washed with alcohol, acetone and water. After drying, 19 g of a yellow pigment which can be used directly in this form for incorporation into lacquers are obtained. The lacquerings aredistinguished by excellent fastness to light and to weathering.

EXAMPLE 3-4 If, in the preceding examples, the 3,4,5,6-tetrachloro-2-cyanobenzoic acid methyl ester is replaced by a corresponding amount of 3,4,5,6-tetrabromo-2- cyanobenzoic acid methyl ester, a yellow pigment with similarly good properties is obtained.

EXAMPLES 5-1 12 The table which follows lists further dyestuffs of the formula R N=N-R l N C1 C1 u g I r C Cl" V c1 NH HN 41 c C I 11 I C1 0 0 Cl which are obtained if a diamine of the formula N.=N-R 1 3,4,5,6-tetrachloro-Zfcyanobcnzoic acid methyl ester. 'C'olun'm 'lV indicates the shade of a lacquer coloration obtained according to Example l 15.

Example No. v R R, Shade 5 l H Yclluw CH3 6 Q r H Yellow OCH:I i Cg H Orange Cl 8 @H H Yellow 7 Yellow- 9 :a H orange l0 Q H Yellow OCH ll 1 Q H Red-brown OCH3 l2 1 H Brown 13 CH ,CONH H I Orange l4 C O-NH H Orange 15 CQ-NH H Orange OCH ,6 CO NH H C H 0C" l7 CONH Q H Brown OCH3 Cl x CONH H Brawn w CH;,-CONH H Brownyellow -continued Example No. R R Shade 20 CH CONH H Ycllowbrown CH 2] Q H Yellow CH 22 Q H Yellow Rcddish- 23 CH H tinged yellow O C H 3 34 Cl- H Orangered OC H 0 CH 25 CH O Q I H Red-brown CI 26 H Yellow Reddish- 27 C H;, H tinged yellow v c H 3 Brownc|-- --CO-NH- H yellow 29 c| CONH H Yellowbrown Rcddish- 30 C H;,CONH H tinged yellow -continued Example No. R R Shade C H C ONH 31 H Orange 32 CH -,CONH H Yellowbrown CH CON H Reddish- 3 3 7 CH H tinged 3 yellow C H CONH 34 Q H Orange OCH 35 C l H Brownyellow C l N H CO Yellow- 36 cl NH C O H brown 37, Q N HCO H Yellow 38 Cl Cl Yellowbrown 39 CH -,CONH Cl Yellow 40 CH;,CONH- Cl Brownyellow CI 41 CONH--- Cl Brownyellow -continued Example No. R R. Shade 42 CH,,CONH- Cl Yellow '43 C] Cl Yellow 44 cl CONH Cl Yellow brown cu 45 (1- ---CONH Cl Yellowbrown 46 Cl zl Brownyellow 47 C H CH3 Yellowbrown 04 48 6 CH3 Yellow c H 3 49 CH;,CONH CH3 Yellow oc H 3 5o CH,,CONH H3 Yellow CH3CONH 5 l CH3 Redorange OCH3 cl 5: CH CoN H- H Brown CH 3 53 CH CONH- Q (3H,, Orange cll I -ohtirii1e'd Example I I 1 R R, Shade CH3 54 CH=;CONH. CH" Yellow 55 OCH;, Orange CH3 56 CH;,CONH Q OCH;, Orange 57 G OCH Orange CH 3 58 C OCH;, Orange 59 Q OCH Orange ocu 60 OCH Brown red 'OCH3 6| 6 OCH:, Orange Cl 62 OCH3 Orange c1 63 OCH:, Redorange Cl 64 CH"(ONH Q O\ H; Brown 65 CONH ocH,. Brownred OCH;| Brown 66 CH:,CONH

67 OC H1, Orange continued Example h No R R Shade 68 -OCH,, Orange 69 CH,, --OCH; Orange 70 -OCH;, Brown orange 7 3 OCH Orungc red 7 0- CONH ocH Orange C H 3 C ON H 75 Q OCH; Orange C H CONN 16 oc|-l=x Red OCH 78 OC H;, Brown Cl 77 Cl-Q -OCH;, Brown -continucd Example No. R R, Shade c H3 v s cH .,coNH OCHF- c| Brown H3 109 Q OCH2CH2OCH;, Orange I cu C H 3 10 Q 004 Q -01 Orange C H3 1 l 1 Q OCH CH O Cl Orange OCHgCHgOCHy- Q Cl Orange EXAMPLE 1 l 3 2 g of the pigment manufactured according to Example 2, 36 g of hydrated alumina, 60 g of linseed .oil varnish of medium viscosity and 0.2 g of cobalt linoleate are mixed, and ground, on a triple-roll mill. The yellow prints produced with this colour paste are distinguished by excellent fastness to light.

EXAMPLE 1 14 0.6 g of the pigment manufactured according to Example 2 and listed under 67 in the table, 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyl tin dilaurate and 2 g of titanium dioxide are mixed and milled for minutes on a triple-roll mill. The colour of the orange polyvinyl chloride films produced therewith is fast to migration, heat and light.

EXAMPLE 1 l5 10 g of titanium oxide and 2 g of the pigment manufactured according to Example 2 and listed in the table under 58 are ground with 88 g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of melamine-formaldehyde resin solids content), 8.8 g of ethylene glycol monomethyl ether and 28.8 g of xylene for 48 hours in a ball mill.

If this lacquer is sprayed onto an aluminium foil, predried for 30 minutes at room temperature and subsequently stoved for 30 minutes at C, an orange lacquering which is distinguished by very good fastness to overlacquering, light and weathering is obtained.

We claim:

1. An iminoisoindolinone dyestuff of the formula wherein R is H or methoxy and Y and Z denote hydrogen, chlorine, alkyl containing 1 to 4 carbon atoms for alkoxy containing 1 to 4 carbon atoms.

2. An iminoisoindolinone dyestuff of the formula CO-NH 1 c1 NH Cl R 1 wherein R denotes hydrogen or methoxy, Y and Z denote hydrogen, chloro, alkyl containing 1 to 4 carbon atoms or alkoxy containing 1 to 4 carbon atoms X and Y denote hydrogen, chloro, alkyl containing l to 4 carbon atoms alkoxy containing 1 to 4 carbon atoms, or trifluoromethyl, and Z denotes hydrogen; chloro, alkyl containing 1 to 4 carbon atoms or alkoxy containing 1 to 4 carbon atoms.

3. An iminoisoindolinone dyestuff of the formula:

wherein R Y and Z have the meaning indicated in claim 4 and R denotes alkyl containing 1 to 3 carbon atoms, phenyl, chloro substituted phenyl, or alkoxy containing 1 to 4 carbon atoms.

4. The compound according to claim 1 of the formula CH N=N 5 ll ll 01 o c 1 NH HN The compound according to claim 1 of the formula CH 3 c 5 0 CH5 c1 11 N 01 u n (:1 c ,0 1

- NH HN Cl C C 1 u u 01 o 0 c1 6. The compound according to claim 1 of the formula CH N=N H 5 Cl N N Cl ll ll 01 c c 1 NH HN Cl C C Clll 0 0 C1 7. The compound according to claim 1 of the formula 8. The compound accordng to claim 1 f the formula 9. The compound according to claim 1 of the formula N= c1 .1 CH O N=N on 01 a Q 5 CONH Cl N N Cl Cl N Cl N u n 01 ll 01 c o 1 01 0 NH m1 NH EN 01 c 0 l 01 c c 01 II n ll 01 O C1. C1 0 0 Cl 

1. AN IMINOISOINDOLINONE DYESTUFF OF THE FORMULA
 2. An iminoisoindolinone dyestuff of the formula
 3. An iminoisoindolinone dyestuff of the formula:
 4. The compound according to claim 1 of the formula
 5. The compound according to claim 1 of the formula
 6. The compound according to claim 1 of the formula
 7. The compound according to claim 1 of the formula
 8. The compound accordng to claim 1 of the formula
 9. The compound according to claim 1 of the formula 